Shrinkproofing wool with polyamides



United States Patent SHRINKPROOFIN G WOOL WITH POLYAMIDES Lowell A.Miller and Robert E. Whitfield, Walnut Creek,

and William L. Wasley, Berkeley, Calif., assignors to the United Statesof America as represented by the Secretary of Agriculture No Drawing.Filed Mar. 27, 1961, Ser. No. 98,718

16 Claims. (Cl. 8-128) (Granted under Title 35, U.S. Code (1952), sec.266) A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

A principal object of this invention is the provision of new methods forshrinkproofing wool. Another object of the invention is the provision ofthe novel products so produced. Further objects and advantages of theinvention will be obvious from the following description wherein partsand percentages are by weight unless otherwise specified.

In the prior art it is suggested that the shrinkage properties of woolcan be improved by applying to the wool fibers a high molecular weightpolyamide such as polyhexamethylene adipamide or similar polyamide ofthe nylon type. This is accomplished in the following mannet: Theselected polyamide is first converted into soluble form, for example, byforming an N-methylolderivative thereof. The N-methylol derivative isapplied to the wool and the treated wool is then immersed inhydrochloric acid whereby the N-methylol polyamide is converted to theunsubstituted polyamide. A primary disadvantage of this known process isthat it is cumbersome and inefficient because it requires procurement ofa preformed polyamide, conversion of this to a soluble form, and finalreconversion to an insoluble form. Particular trouble is encountered inthe last step where extended contact with acid is required toinsolubilize the coating of N-methylol polyamide. Unless this acidtreatment is complete, the polyamide will remain soluble and be removedfrom the textile when it is washed.

In accordance with this invention, a pre-formed polyamide is not usedbut a polyamide (or other condensation polymer) is formed in situ on thewool fibers. This is accomplished by serially applying to the wool thecomplementary agents required to form the desired polymer, theseagents-in the preferred modification of the invention--being dissolvedin mutually-immiscible solvents. Thus in a typical embodiment of theinvention the wool is first impregnated with an aqueous solution of adiarnine and then impregnated with a solution of a diacid chloride in awater-immiscible solvent such as carbon tetrachloride. Generally, thesolutions are applied in the order given above, however, the reverseorder gives good results and it is within the ambit of the invention toapply the solutions in either sequence. By serial application of thesesolutions to the fabric, each fibrous element is coated with a two-phasesystem, for example, an inner layer of diarnine in water and an outerlayer of diacid chloride in water-immiscible solvent. Under theseconditions the diamine and diacid chloride react almost instantaneouslyat the interface be'twcenthe phases, producing in situ on the fibers ahigh molecular weight, resinous polyamide whichcoats the fibers andrenders them shrinkproof. By suitable selection of the complementaryreactants other condensation polymers such as polyurethanes, polyureas,polyesters, polycarbonates, or various interpolymers "thereof can beformed in situ on wool fibers. The polymer formed is insoluble so thatthe shrinkproofing effect is durable; it is retained even after repeatedwashings with soap and water or detergent and waterformulations.

3,078,138 Patented Feb. 19, 1963 A feature of the invention is that thehigh molecular weight resinous polymers are formed in many cases atordinary (room) temperature, which is in sharp contrast to the muchhigher temperatures required in the conventional melt condensations usedin preparing polyamides, polyurethanes, etc. For example, in the usualpreparation of polyamides by melt procedures, temperatures of over 200C. are customarily employed.

As noted above, the treatment in accordance with the invention rendersthe treated wool essentially shrinkproof so that garments produced fromthe treated wool may be laundered in conventional soap and water ordetergent and water formulations with negligible shrinking or felting.Further, the treated wool or garments prepared therefrom are in theeasy-care category in that after washing and tumble drying, they arequite free from wrinkles so that they require only a minor amount ofpressing. An important .ppint to be stressed is that the shrinkproofingeffect is secured without damage to the hand of the fabric. That is, thetreated fabric retains its normal hand so that it is useful for all theconventional applications in fabricating garments as is untreated wool.Other items to be mentioned are that the treatment does not cause anydegradation of the wool so that there is no significant loss of tensilestrength, abrasion resistance, resiliency, elasticity, etc. Moreover,since the polymer is formed in situ on the fibers-in contrast to systemswherein polymers arespread en masse over the face of a fabric-'there issubstantially no loss of porosity of the fabric. A further item is thatthe treated wool may be dyed with conventional wool dyes to obtainbrilliant, level dyeings.

.A particular feature of the invention and one that emphasizes itssimplicity is that no heat-curing step is required. Followingapplication of the two solutions, the textile merely needs to be rinsedor washed. Then, after drying, it is ready for use or sale.

The invention is applicable to wool in any physical form, for example,bulk fibers, slivers, rovings, yarns, felts, woven textiles, knittedtextiles, or even completed garments or garment parts.

A remarkable feature :of the invention is that the polymers fiormed onthe wool fibers are not merely physical coatings; they are chemicallybonded to the wool, that is, the added polymer .is grafted onto thewool. The fact that a chemical bonding is achieved rather than a merephysical adhesion has been demonstrated by experiments wherein it wasattempted to dissolve the grafted polymer with solvents which arecapable of dissolving the polymers in bulk. Thus, wool cloth wasserially impregnated with (1) an aqueous solution of hexamethylenediamine and (2) a solution of sebacoyl chloride in carbon tetrachloride.The treated wool was rinsed in water and dried in air. It was foundthatthe wool had a polyamide resin uptake of 4.4% and showed an areashrinkage of 1% on being subjected to a very severe washing test.Samples of this treated wool were subjected to these tests:

(a) A-sample of the treated wool was extracted for 6 hours with benzylalcoholv at.910 .C.

(b) Another sample of the treated wool was extracted with formic acid(98% first for 2 hours at 70 C., then at 35 C. for 22 hours.

(c) The extracted wool samples were treated to evaporate the solventsand weighed to determine the possible loss of resin. Also, the extractedsamples were again subjected tothe same severe washing test to determinetheir shrinkage. It was found 'that'there was no measurable decrease inweight, indicating no loss of polyamide by the'wool and, moreover, thearea shrinkage was still 1% or .less, further-.indicating-that there wasno loss of polyamide. It may be noted that both benzyl alcohol and 98%formic acid are good solvents for fiberforming polyamides such aspolyhexamethylene sebacamide and had the polyamide on the wool beenmerely a coating, the extraction would have resulted in a weight lossand a marked increase in the percentage of shrink- The mechanism bywhice the graft polymerization occurs is believed to involve a reactionof functional groups on one or the other of the complementary agentswith the free amino or hydroxy groups present in the wool molecule,these reactions giving rise to such linkages as amide, ester, urea,urethane, carbonate, etc. which chemically unite the wool with thepolymer. Thus the case of graft polyamides can be postulated by thefollowing idealized formulas:

CRONH-R-N]I W o L J In the above and succeeding formulas, W representsthe polypeptide chain of the wool, containing prior to the reaction,free amino (NH or free hydroxy (-OH) groups. R and R are bivalentorganic radicals (representing in this case the residues of the diamineand diacid chloride, respectively), and n represents the number ofpolyamide repeating units.

The above formulas are obviously simplified and idealized as thepolyamide chains may be attached at both their ends to a single woolmolecule or they may crosslink together different wool molecules throughamide or ester linkages. The important point from a practical andrealistic view is that chemical bonding of the polyamide to the wool hasbeen demonstrated and the theoretical nature of the mechanism of bondingis not of real concern to the invention.

The invention encompasses the grafting of other types of polymersbesides polyamides onto the wool molecule. Typical polymers which may beapplied in accordance with the invention are polyurethanes, polyureas,polyesters, polycarbonates, and interpolymers wherein the recurringunits contain two or more different units of the classes of amide,urethane, urea, ester, and carbonate. The grafting of typical examplesof these different types of polymers onto wool are shown in the formulasbelow, again following an idealized plan:

Polyurethane grafted to wool through urethane or carbonate linkage:

L Jr.

Polyurea grafted to wool through urea or urethane linkage:

Polycarbonate grafted to wool through urethane or carbonate linkage:

Copoly (amide-urethane) grafted to wool through amide or ester linkage:

wherein Z is oxygen or sulphur. The term non-0x0 is used in the usualsense of excluding aldehyde and ketone configurations. The non-0x0carbonyl group may occur in various types of combinations, illustrativeexamples of which are given below.

Amide:

Z JLI L Urethane:

z L Urea:

2 ---NH-- i k-NH- Ester:

Z Carbonate:

z z-- z (Z being sulphur or oxygen).

GENERAL CONSIDERATIONS In the practice of the invention, selection isfirst made of the appropriate complementary agentsherein termedComponent A and Component B-required to form the desired polymer on thewool fibers. The interrelationship between the nature of the agents tobe used as Components A and B and the type of polymer produced isexplained in detail below in connection with the various modificationsof the invention. However, it is apropos to mention at this point thatin general, Component A may be a diamine, a diol, or a mixture of adiamine and a diol.

Dependant on the materials selected for Component A, Component B may be,for example, a diacid chloride, at bischloroformate, a diisocyanate, ormixtures of these classes of compounds. Since Components A and B may beselected to form any desired type of condensation polymer, thesecomponents may be aptly termed as complementary organic condensationpolymer-forming intermediates. They may further be appropriatelydesignated as fast-reacting or direct-acting because they form theresinous polymers rapidly and directly on contact without requiring anyafter-treatments, such as treatment with curing agents, oven cures, etc.

Having selected the desired Components A and B, these are formed intoseparate solutions for application to the wool to be treated. Anessential consideration in the preferred modification of the inventionis that the solvents used in the respective solutions of Components Aand B be substantially mutually immiscible so that a liquid-liquidinterface will be set up between the two solutions on the wool fibers.Thus, for example, Component A is dissolved in water and Component B isdissolved in benzene, carbon tetrachloride, toluene, xylene, ethylenedichloride, chloroform, hexane, octane, petroleum ether or othervolatile petroleum distillate, or any other inert water-immisciblesolvent. The two solutions are then applied to the wool serially, thatis, the wool is treated first with one solution then with the other. Theorder of applying the solutions is not critical. Generally, the solutionof Component A is applied first and the solution of Component B isapplied next; however, the reverse order gives good results and it iswithin the ambit of the invention to apply the solutions in eithersequence.

The solutions may be applied to the wool in any desired way as long asthey are applied serially. A preferred method involves immersing thewool in one solution, removing excess liquid as by use of squeeze rolls,immersing the wool with the second solution, again removing excessliquid, rinsing the treated fabric in water and then drying it.Conventional apparatus consisting of tanks, padding rolls, squeeze rollsand the like are generally used in applying the respective solutions.The amount of each solution applied to the textile may be varied byaltering the residence time in the solutions, the pressure exerted bythe squeeze rolls and by varying the concentration of the activematerials in the respective solutions. To decrease carry-over of thesolvent from the first treating solution to the second solution, thewool after its immersion in the first solution may be subjected todrying conditions such as a current of warm air to concentrate thesolution carried by the Wool.

As noted above, a critical factor in the preferred form of the inventionis that the complementary-agents-Component A and Component B-areserially applied to the textile dispersed in solvents which aresubstantially mutually immiscible. The nature of the solvents is of noconsequence as long as they are essentially inert and possess theabove-stated property of substantial immiscibility. Usually volatilesolvents are preferred as they may be removed from the treated textileby evaporation. However, non-volatile solvents can be used, in whichcase they may be removed from the product by extraction with suitablevolatile solvents therefor or Washed out with soap and water ordetergent and water formulations. In many cases the ingredients ofComponent A are soluble in water and may thus be applied to the textilein aqueous solution. In such case the solvent for Component B may be anyinert, essentially water-immiscible organic solvent. Typicalillustrative examplies thereof are benzene, toluene, xylene, carbontetrachloride, ethylene dichloride, chloro form, hexane, octane,petroleum ether or other volatile petroleum fraction. It is, however,not essential that Component A be employed in aqueous solution. Thus,one may utilize a system of two essentially immiscible organic solvents,Component A being dispersed in one solvent and Component B in the other.As an example,

Component A may be dispersed in Z-bromoethyl acetate and Component Bdispersed in benzene. Another example involves using formamide,dimethylformamide, or diethylformamide as the solvent for Component Aand using nhexyl ether as the solvent for Component B. A further exampleinvolves a system of adiponitrile as the solvent for Component A andethyl ether as the solvent for Component B. Examples of other pairs ofsolvents which are substantially immiscible with one another and whichmay be used for preparing the solutions of the respective reactants are2-bromoethyl acetate and n-hexyl ether, ethylene glycol diacetate andn-hexyl ether, adiponitrile and n-butyl ether, adiponitrile and carbontetrachloride, benzonitrile and formarnide, n-butyl ether andformarnide, di-N-propyl aniline and formamide, isoamyl sulphide andformamide, benzene and formamide, butyl acetate and formamide, benzeneand nitromethane, n-butyl ether and nitromethane, carbon tetrachlorideand formamide, dimethyl aniline and formamide, ethyl benzoate andformamide.

In cases where Component A is a diamine and/ or a diol in the form ofits alkali-metal salt, the solvents therefor may contain hydroxy groups.Because amine, alcoholate, and phenolate groups are so much morereactive than hydroxy groups, there will be little if any interferenceby reaction of the hydroxy groups of the solvent with the active agentsof Component B, particularly if the solutions of the reactants are atordinary temperatures. In such event, then, solvent pairs of thefollowing types may be employed: Diethylene glycol rnonomethyl ether andnhexyl ether, diethylene glycol monoethyl ether and n-hexyl ether,2-ethylhexanol and adiponitrile, isoamyl alcohol and adiponitrile,glycerol and acetone, capryl alcohol and formamide, ethylene glycol andbenzonitrile, diacetone alcohol and di-N-propylaniline, Z-ethylhexanoland formamide, triethylene glycol and benzyl ether.

The concentration of active materials (Component A and Component B) inthe respective solutions is not critical and may be varied widely.Generally, it is preferred that each of the pair of solutions containsabout from 1 to 20% of the respective active component. In applying theprocess of the invention, enough of the respective solutions are appliedto the wool to give a polymer deposit on the fibers of about 1 to 10%.Such amounts provide a substantial degree of shrinkproofing with nosignificant reduction in hand of the wool. Greater amounts of polymermay be deposited on the fibers if desired but tend to change the naturehand of the wool. Also, thicker deposits are likely to containsubstantial amounts of non-grafted polymer. The relative amounts ofComponent A and Component B applied to the wool may be varied as desiredfor individual circumstances. Generally, it is preferred to apply thecomponents in equimolar proportions, that is, the amounts are soselected that there are the same number of functional groups provided byComponent A as provided by the functional groups or" Component B.

It is often desirable to add reaction promoters or catalysts to eitherof the solutions of Component A or B in order to enhance reactionbetween the active agents. For example, in cases where the systeminvolves reaction between a diamine (or a-diol) and a diacid chloride ora bischloroformate it is desirable to add to either of the solutions asufficient amount of alkaline material to take up the HCl formed in thereaction. For such purpose one may use a tertiary amine such aspyridine, dirnethyl aniline, or quinoline or an alkalimetal hydroxide,or, more preferably, an alkaline material with buffering capacity suchas sodium carbonate, sodium bicarbonate, trisodium phosphate, borax,etc. Another plan which may be used in instances where Component Aincludes a diamine and Component B includes a diacid chloride orbischloroformate, involves supplying the diamine in excess so that itwill act both as a reagent and as an -HClacceptor. The reaction ofComponents A and B may also be catalyzed by addition of such agents astributyl tin chloride, stannous tartrate, ferric chloride, titaniumtetrachloride, boron trifluoride-diethyl ether complex, or tin salts offat acids such as tin laurate, myristate, etc. Such catalysts areparticularly useful to promote reaction between (1) diols and (2)diisocyanates, diacid chlorides, and bischloroformates.

Where one of the solutions of the reactants contains water as thesolvent, it is often desirable to incorporate a minor proportion of asurface-atcive agent to aid in dispersing the reactant and to assist inpenetration of the solution into the textile. For this purpose one mayuse such agents as sodium alkyl (C -C sulphates, the sodium alkane(cg-C13) sulphonates, the sodium alkyl (C -C benzene sulphonates, estersof sulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps,typically sodium salts of fat acids. Emulsifying agents of the non-ionictype are suitable, for example, the reaction products of ethylene oxidewith fatty acids, with polyhydric alcohols, with partial esters of fattyacids and polyhydric alcohols or with alkyl phenols, etc. Typical ofsuch agents are a polyoxyethylene stearate containing about 20oxyethylene groups per mole, a polyoxyethylene ether of sor-bitanmonolaurate containing about 16 oxyethylene groups per mole, adistearate of polyoxyethylene ether of sorbitol containing about 40oxyethylene groups per mole, iso-octyl phenyl ether of polyethyleneglycol, etc. Generally, only a small proportion of surface-active agentis used, on the order of 0.05 to 0.5%, based on the weight of thesolution. In addition to, or in place of the surface-active agent, asupplementary solvent may be added to the primary solvent (water) inquantity sufficient to disperse the active reactant. For such purposeone may employ acetone, or other inert volatile solvent, particularlyone that is at least partially miscible with water. It is evident thatthe solutions of Components A and B need not necessarily be truesolutions; they may be colloidal solutions, emulsions, or suspensions,all these being considered as solutions for the purposes of the presentinvention.

Ordinarily, the treatment of the wool with the solutions of thecomplementary agents is carried out at room temperature as at suchtemperature the polymerization takes place very rapidly, that is, in amatter of a minute or less. If, however, a higher rate of polymerizationis desiredas in continuous operation on long lengths of cloth--thesecond solution may be kept hot, for example, at a temperature up toaround 150 C. Also, where the agents used include a diol as such (incontrast to the alkali salt thereof) it is preferable to heat the secondsolution as the polymerization rates with the diols are generallyunsatisfactory at room temperature.

As has been explained above, in the preferred modification of theinvention the solutions of Components A and B--the complementarycondensation polymer-forming intermediatesare serially applied to thewool in the form of mutually-immiscible solutions to provide aliquid-liquid interface between the solutions as they are serially laidonto the fibers. In a less preferred modification of the invention, asystem is used which utilizes a solid-liquid interface. Such a system isestablished in the following way: The wool is first impregnated with asolution of one of the complementary agents-for example, ComponentA-dispersed in an inert volatile sol vent. The Wool is then subjected todrying as by subjecting it to a current of hot air. The wool fiberswhich are now covered with a deposit of the first component in a solidstate, are then impregnated with the complementary agent-Component B, inthis case, dispersed in an inert, preferably volatile solvent. In thisway the fibers are layered with a superposed system of solid component Aand a solution of Component B. Under these conditions polymerizationtakes place rapidly forming the polymer in situ on the fibers andgrafted thereto. In

this system it is not essential that the respective solvents beimmiscible. Thus, for example, Component A may be applied in watersolution and Component B in a watermiscible solvent such as dioxane oracetone. A typical example of practicing this modification involvesimmersing the wool in an aqueous solution of a diamine and anHcl'acceptor, removing the wool from the solution, squeezing it throughrolls to remove excess liquid, subjecting it to a draft of hot air untilthe wool is dry to the touch (about 10-20% moisture in the impregnatedwool) and then immersing the wool in a solution of a diacid chloridedissolved in an inert, volatile solvent. The wool is then removed fromthis second bath, squeezed through rollers to remove excess water,rinsed, and dried in air. though this system is operative, it is not apreferred technique because the polymerization at the solid-liquidinterface is slower and less uniform in degree of polymerization and thedegree of shrinkproofing afforded to the wool per unit weight of polymerformed on the fibers is less than with the system of mutuallyimmisciblesolutions.

COMPONENTS A AND B As noted briefly above, the selection of Components Aand B depends on the type of polymer desired to be formed on the woolfiber and grafted thereto. In general, Component A may be a diamine, adiol, or a mixture of a diamine and a diol; Component B may be a diacidchloride, 21 bischloroformate, a diisocyanate, or a mix ture of two ormore of these classes of compounds. Typical examples of compounds whichcan be employed as Component A in a practice of the invention aredescribed below.

As the diamine one may employ any of the aromatic, aliphatic, orheterocyclic compounds containing two primary or secondary amine groups,preferably separated by at least two carbon atoms. The diamines may besubstituted if desired with various non-interfering (nonfunctional)substituents such as ether radicals, thioether radicals, tertiary aminogroups, sulphone groups, fluorine atoms, etc. Typical compounds in thiscategory are listed below merely by way of illustration and not by wayof limitation. Ethylene diamine, trimethylene diamine. tetramethylenediamine, hexamethylene diamine, octarnethylene diamine, decamethylenediamine, N,N'-dimethyl-1,3-propanediamine, 1,2-diamino 2 methylpropane,2,7-diamine-2,o-dimethyloctane, N,N'-dimethyl-1,6- hexanediamine,1,4-diarnino cyclohexane, 1,4-bis(aminomethyl) cyclohexane,2,2-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide,bis(4--aminocyclohexyl) methane, N,N dimethyl 2,2,3,3,4,4hexafluoropentane-1,5-diamine, ortho-, meta-, or para-phenylene diamine,benzidine, xylylene diamine, m-toluylene diamine, ortho-tolidine,piperazine, and the like. If desired, mixtures of different diamines maybe used. It is generally preferred to use aliphatic alpha, omegadiamines, particularly of the type wherein n has a value of 2 to 12,preferably 6 to 10.

As the diol one may employ any of the aliphatic, aromatic, orheterocyclic compounds containing two hydroxy groups, preferablyseparated by at least two carbon atoms. The diols may be substituted ifdesired with various non-interfering (non-functional) substituents suchas ether groups, sulphone groups, tertiary amine groups, thioethergroups, fluorine atoms, etc. Typical compounds which may be used arelisted below merely by Way of illustration and not limitation: Ethyleneglycol, diethylene glycol, 2,2-dimethyl propane-1,3-diol,propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol,decane- 1,10-diol, dodecane-1,12-diol, butane-1,2-diol, hexane-1,2-diol, l-O-methyl glycerol, Z-O-methyl glycerol, cyclohexane-1,4-diol,hydroquinone, resorcinol, catechol, bis

(parahydroxyphenyl) methane, 1,2-bis'(par'ahydroxyphenyl) ethane,2,2-bis(parahydroxyphenyl) propane, 2,2-bis(parahydroxyphenyl) butane,4,4-dihydroxyb'enzophenone, naphthalene-1,5 diol, biphenyl-4,4'-diol,2,2- bis(3-methyl-4-hydroxyphenyl) propane,2,2-bis(3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis(4-hydroxy-dibrornophenyl) propane, etc. If desired, mixtures ofdifferent diols may be used. It is also within the purview of theinvention, though less preferred, to use the compounds containing morethan two hydroxy groups as for example, glycerol, diglycerol,hexanetriol, pentaerythritol, etc. Moreover, it is within the spirit ofthe invention to utilize the sulphur analogues of the diols. Thus, forexample, instead of using the compounds containing two hydroxy groupsone can use the analogues containing either (a) two -SH groups or (b)one -SH group and one O-H group.

Among the preferred compounds are the aliphatic diols, for example,those of the type:

wherein n has a value from 2 to 12. Another preferred category ofaliphatic compounds are the polyethylene glycols, i.e.:

wherein n has a value from zero to 10. A preferred category of aromaticdiols are the bisphenols, that is, compounds of the type D no W itwherein RC-R represents an aliphatic hydrocarbon group containing 1 to12 carbon atoms and R represents hydrogen or a lower alkyl radical. Inthis category especially preferred compounds are2,2-bis(parahydroxyphenyl) propane, often designated as bisphenol-A;2,2- bis(3-methyl-4-hydroxypheny1) propane;2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and brominated derivativesof bisphenol A, such as 2,2-bis(4-hydroxy-dibromophenyl) propane.

The diols are employed as such or in the form of their alkali-metalsalts, that is, as alcoholates or phenolates, depending on whether thediols are aliphatic or aromatic. The alkali-metal derivatives arepreferred as they will react with the active agents of Component B atroom temperature. With the diols, as such, temperatures above roomtemperature are generally required to promote reaction with theircomplements in Component B. In such case proper temperature for thereaction can be achieved by holding the second solution into which thetextile is immersed ,at about 50 to 150 C. It is obvious that thesolvent selected for the second solution will need to be one which has aboiling point above the temperature selected, or, in the alternative, apressurized system can be used to maintain the solvent in the liquidphase.

In the modification of the invention wherein water is used as thesolvent for Component A (a diol in this case) and Component B isdispersed in a water-immiscible, inert solvent, it is preferred to usearomatic diols in their salt (phenolate) form. This affords severaldistinct advantages. Thus the alkali-metal phenolates are quite solublein water, they are relatively stable in aqueous solution (in contrast tothe alcoholates), and they will react at room temperature with diacidchlorides, bischloroformates, or diisocyanates so that no heating isrequired.

Typical examples of compounds which can be employed as Component B in apractice of the invention are described below.

As the diacid chloride one may employ any of the aliphatic aromatic, orheterocyclic compounds containing two carbonylchloride (-COCl) group,preferably separated by at least two carbon atoms. the diac i'dchlorides may be substituted if desired with non-interfering(nonfunctional) substitutents such as ether groups, thioether groups,sulphone groups, etc. Tyical examples of compounds in this category arelisted below merely by way of illustration and not limitation: 'Oxalylchloride, maleyl chloride, fumaryl chloride, malonyl chloride, succinylClCOCH -'CH="CH-'CH COCI diglycollic acid chloride, i.e., O'(CH -COCl)higher :hornologues of this compound as O(CH -CH COCl)'dithiodiglycollic acid chloride, diphenylolpropan'e-diacetic chloride,i.e., (CH C(C H ,OCH COCD and the like. If desired, mixtures ofdifferent diacid chloride may be used. It is also evident that thesulphur analogues of these compounds may be used and are included withinthe spirit of the invention. Thus, instead of using compounds containingtwo --COC1 groups one may use compounds containing one -CSCl and one-COC1 group or compounds containing two "CSCl groups. Moreover, althoughthe diacid "chlorides are preferred as they are reactive and relativelyinexpensive, the corresponding bromides and iodines may be used As thediacid chloride, it is generally preferred to use the aliphaticcompounds containing two carbonylchloride groups in alpha, omegaposition, particularly those ofthe type:

ClCO' CH CO Cl wherein n has a value from 2 to 12. Another preferredcategory "includes the compounds of the formula ClCO-ACOC1 (where A isthe benzene or cyclohexane radical), especially para-substitutedcompounds such as terephthalyl and hexahydroterephthalyl chlorides.

As the bischloroformate one may use any of the aliphatic, aromatic, orheterocyclic compounds containing two chloroformate groups preferablyseparated by at least two carbon atoms. The bischloroformates may besubstituted if desired with nonphone groups, ether groups, thioethergroups, etc. interfering (non-'fuctional) substituent-s such as sul-Typical examples of compounds in this category are listed below merelyby way of illustration and not limitation: Ethylene glycolbischloroformate, diethylene glycol bischloroformate, 2,2-dimethylpropane 1,3-diol bischloroformate, propane-1,3-diol bischloroformate,butane-1,4- diol bischloroformate, hexane-1J6-diol bischloroformate,octane-1,8-diol bischloroformate de'cane-LlO-dio1 bischloroformate,butane-1,2-diol 'bischloroforrnate, hexanel,2-diol bischloroforrnate,2-methoxyglycerol 1,3 bischloroformate, glycerol-1,2-bischloroformate,glycerol-l, 3-bischloroformate, diglycerol bischloro formate,hexanetriol bischloroformate, pentaeryt hritol bischloroformate,cyclohexane-lA-diol bischlo'roformate, hydroquinone bischloroformate,resorcinol bischloroformate, catechol bischloroformate, bischloroformateof 2,2-bis (parahydroxyphenyl) propane, bischlor'oformate of 2,2-bis(parahydroxyphenyl) butane, "bischloroformate of4,4'-dihydroxybenzophenone, bischloroformate of1,2-bis(parahydroxyphenyl) ethane, naphthalene- 1,5-diolbischloroformate, biphenyl-4,4'-diol bischloroformate, etc. If desired,mixtures of diiferentbischloroformates may be used.

Among the preferred compounds are the aliphatic bischloroformates, forexample, those of the type:

wherein n has a value from-2to 12. Another preferred 11 category ofcompounds are the bis-chloroformates derived from polyethylene glycols,e.g.,

ClC O-CH:-CH:-[O oHl-oHi ]n-o Ora-crn-o'b-m wherein n has a value fromzero to 10. A useful category of aromatic bischloroformates are thebisphenol chloroformates, that is, compounds of the type:

R R R r Q it 01-60 it oo-o1 wherein R-CR represents an aliphatichydrocarbon group containing 1 to 12 carbon atoms and R is hydrogen or alow alkyl radical.

It is also evident that the sulphur analogues of the hischloroformatesmay be used and such are included within the spirit of the invention.Thus, instead of using the compounds containing two groups one may useany of the compounds containing the sulphur analogues of these groups,for example, the compounds containing two groups of the formula X-("JClwherein one X is sulphur and the other is oxygen or wherein both Xs aresulphur. Moreover, although the bichloroformates are preferred becausethey are reactive and relatively inexpensive, it is not essential thatthey contain chlorine and one may use the corresponding bisbromoformatesor bisiodoformates.

As the diisocyanate one may employ any of the aliphatic, aromatic, orheterocyclic compounds containing two isocyanate (NCO) groups,preferably separated by at least two carbon atoms. The diisocyanates maybe substituted if desired with non-interfering (nonfunctional)substituents such as ether groups, thioether groups, sulphone groups,etc. Typiial examples of compounds in this catagory are listed belowmerely by way of illustration and not limitation: Ethylene diisocyanate,propylene diisocyanate, butylene diisocyanate, trimethylenediisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,octamethylene diisocyanate, decamethylene diisocyanate, cyclohexylenediisocyanate, bis- (2-isocyanatoethyl) ether, bis (2-isocyanatoethyl)ether of ethylene glycol, o-phenylene diisocyanate, m-phenylenediisocyanate, p-phenylene diisocyanate, tolylene-2,4-diisocyanate,tolylene-L6-diisocyanate, 3,3'-bitolylene-4,4-diisocyanate, i.e.,

CH; GB:

diphenyl ether-4,4'-disocyanate, i.e.,

3, 5, 5-bixylylene-4,4-diisocyanate, i.e.,

l R (R is-CH diphenylmethane-4,4'-diisocyanate, i.e.,

biphenylene diisocyanate, 3,3-dimethoxy-biphenylene- 4,4'-diisocyanate,naphthalene diisocyanates, polymethyl polyphenyl isocyanates, etc. It isalso evident that the .sulphur analogues of these compounds may be usedand such are included within the spirit of the invention. Thus forexample, instead of using the compounds containing two --NCO groups onemay use their analogues containing either two -NCS groups or one NCOgroup and one NCS group. Another point to be made is that it is withinthe spirit of the invention to utilize the derivatives which yield thesame products with compounds containing active hydrogen as do theisocyanates. Particular reference is made to the biscarbamyl chlorideswhich may be used in place of the diisocyanates. Thus one may use any ofthe above-designated compounds which contain carbamyl chloride groups IN-d-o1) or their sulphur analogues in place of the isocyanate groups.

Among the preferred compounds are the aliphatic dnsocyanates, forexample, those of the type wherein n has a value from 2 to 12. Otherpreferred compounds are the toluene diisocyanates, xylylenediisocyanates, and diphenylmethane-4,4'-diisocyanate which may also betermed methylene-bis(p-phenylisocyanate).

There has been set forth above a comprehensive disclosure of thepreferred types of complementary agents, that is, diamines, diols,diacid chlorides, bischloroformates, diisocyanates, and theirequivalents. Although it is preferred to use these agents for optimumresults, they are by no means the only compounds which may be used. Theinvention in its broadest aspect includes the application of many othertypes of complementary agents which have the ability to formcondensation polymers when applied to Wool by the disclosed procedures.V arious examples are thus set forth of other types of compounds whichmay be used.

Polysulphonamides-f0rmed by conjoint use 0) a diamine and a disulphonylchloride.A typical example in this category involves applying to thewool an aqueous solution of a diamine, followed by applying to the woola disulphouyl chloride dissolved in benzene, toluene, or other inert,essentially water-immiscible solvent. Any of the diamines abovedescribed may be used in conjunction with such disulphouyl chlorides asbenzene-1,3-disulphonyl chloride, biphenyl-4,4'-disuiphonyl chloride,toluene disulphouyl chlorides or aliphatic compounds such as those ofthe formula wherein n has a value from 2 to 12. Related polymers can beformed by applying these disulphouyl chlorides (as Component B) inconjunction with such compounds as urea, guanidine, thiourea, biuret,dithiobiuret, or the like as Component A.

Polysulphonates-formed by the conjoint use of a dial and a disulphouylchloride-In a typical example in this area, an aqueous solution of adiol-preferably in the form of its alkali-metal saltis first applied tothe Wool, followed by application of a disulphouyl chloride in inert,essentially Water-immiscible solvent. For this purpose one may use anyof the diols and disulphouyl chlorides exemplified above. A variant ofthis procedure is to use the corresponding dithiol in place of the diol,thus to form a polythiolsulphonate.

An alternative to the diacid chlorides is the use of mixed anhydrides ofthe corresponding dicarboxylic acids with monobasic acids such astrifluoroncetic acid, clihutylphosphoric acid, or the like. Such mixedanhydrides may be employed, for example, as Component B in conjunctionwith a diamine, diol, or dithiol as Component A to 13 form polyamides,polyesters, or polythiolesters, respectively.

Another plan involves the use of urea, thiourea, biuret, dithiobiuret,guanidine, or the like (as Component A) in conjunction with diacidchlorides as Component B to form polyureas, polythioureas, etc.

Having now described the types of compounds which may be used asComponents A and B, we will next explain how these compounds may beselected in various combinations to form the preferred types of polymersin situ on wool fibers and grafted thereto.

EMBODIMENT 1 In this preferred embodiment of the invention, Component Ais a diamine and Component B is a diacid chloride. B-y such selection ofthe complementary agents, polyamides are deposited on the wool fibersand grafted thereto.

Particularly desirable features of this embodiment 1 of the inventionare that a high degree of shrinkproofing is attained with a low level ofpolymer formed on the fiber. Moreover, the process is especially simplebecause the serial treatments may be carried out at ordinary (room)temperature, the polyamide being formed virtually instantaneously undersuch conditions.

Numerous variations of the basic procedure of this embodiment willsuggest themselves to those skilled in the art in the application ofEmbodiment l of the invention, without departing from the fundamentalsof the invention. Some of these variations are explained below.

If desired, one may prepare a prepolymer containing internal amide unitsand terminal amine groups. Such prepolymers can be prepared, forexample, by reacting in known manner a molar excess of diamine with adiacid chloride. The prepolymer would then be used as Component A whilefor Component B one would use a diacid chloride. A typical example ofprocedure in this area would be to use as Component A a prepolymer ofthe type.

and to use as Component B a diacid chloride (C1CORCOCl) thus to producea polyamide containing repeating units of the type 0 o 0 -HN-RNH"J-R'iNH-RNH- n"-ti- (In these formulas, R, R, and R represent bivalentorganic radicals.)

In the alternative, one may prepare a prepolymer containing internalamide groups and terminal carbonylchloride (-COCl) groups. Such aprepolymer used as Component B in conjunction with a diamine asComponent A, would yield a polyamide similar to that shown above.

It is evident from the foregoing description that there is a very widechoice available in the selection of the complementary agents (diamineand diacid chloride) so that generically the pol-yamides deposited onthe wool and grafted thereto will contain repeating units of the typewherein R represents a bivalent organic radical; Z represents an oxygenor sulphur atom; R represents a bivalent organic radical or a bondlinking the two carbonyl groups; and the two xs taken separatelyrepresent two hydrogen atoms or two monovalent organic radicals, ortaken together the xs represent a single bivalent organic radicallinking the two nitrogen atoms to which they are attached. In thepreferred modifications of the invention, Z is oxygen; R and R representbivalent hydrocarbon radicals or bivalent hydrocarbon radicalsinterrupted by internal ether (-O--) linkages; and x is hydrogen. In theespecially preferred modifications of the invention, the reactants areso chosen that R and R represent bivalent hydrocarbon radicalscontaining at least two carbon atoms.

Coming under special consideration, particularly because of theexceptionally high shrink resistance obtained with a very smallpercentage of polyamide, are the use (as Component A) of aliphaticalpha, omega diamines, particularly of the type wherein n has a valuefrom 6 to 10 and the conjoint use (as Component B) of the aliphaticcompounds containing two carbonylchloride groups in alpha, omegapositions, particularly those of the type wherein n has a value from 4to 10. Typical examples are the conjoint use of (A) hexamethylenediamine with (B) s'ebacyl chloride or adipyl chloride. p

This Embodiment l of the invention is further demonstrat'ed by thefollowing illustrative examples. I

Standard shrinkage tests.The tests for shrinkage referred to below wereconducted in the following way: The wool samples were milled at 1700r.p.m. for 2. minutes at 40-42 C. in an Accelerotor with 0.5% sodiumoleate solution, using a liquorto-wool ratio of 50 to 1. After thiswashing operation the samples were measured to 'determine their areaand. the shrinkage was calculated from the original area. With thiswashing method, samples of control (untreated) wool gave an areashrinkage of 45%. The Accelerotor is described in the American DyestuffReporter, vol. 45, p. 685, Sept. 10, 1956.

Example 1 A. A solution Was prepared containing 8.8 grams ofhexamethylene diamine and 0.2 gram of a commercial wetting agent, theisooctylphenyl ether of polyethylene glycol, per 100 ml. water. 7

B. A solution was prepared containing 2 ml. sebacoyl chloride per 100ml. carbon tetrachloride.

A sample of wool cloth was immersed in solution A for seconds, runthrough squeeze rolls to remove excess liquid, immersed for 90 secondsin solution B, run through squeeze rolls to remove excess liquid, rinsedin water, and dried in air at room temperature. The treated wool had apolyamide resin uptake of 8.3% and on Washing exhibited an areashrinkage of 3%.

The procedure as described immediately above was repeated with variationas to sequence of application of the two solutions and time of residenceineach. The conditions used and the results of these experiments and thefirst are tabulated below.

TABLE I Order of Residence Resin up- Area Run applying time in each takeby shrinka e,

solutions solution, wool. percent seconds percent Example 1-A A sampleof the treated wool prepared as described above in Example 1, run 3, anda sample of the untreated wool (control) were subjected to a series oftests to compare the properties of the two materials. The results aretabulated below.

acra ae l Cantilever procedure, AS'lM D-l388-55T.

1 ASTM test method D-l295-53T.

3 ASTM method 13-39-40, 1-inch wide strip.

Sample immersed in 4 M IiOl for 1 hour at 65 C, then weight-lossdetermined as measure of acid solubility.

5 Sample immersed in 0.1 M NaOI-l for 1 hour at 65 C, then weightlossdetermined as measure of alkali solubility.

Sample immersed in 2% pcrecetie acid for 24 hours at 25 0, then treatedwith 0.3% ammonia for 2% hours at 25 C. The weight-loss is thendetermined as a measure of peracetic acid-N33 solubility.

Example 2 W001 cloth was treated as described in Example 1 withvariation in sequence of applying the two solutions and residence timein these solutions. In this case, solution A was as in Example 1;solution B still contained 2 ml. of scbacoyl chloride in 100 ml. solventbut the nature of the solvent was varied as indicated below. Theconditions used and results obtained are tabulated as follows:

TABLE II Solvent in Order of Residence Resin Area Run sebacoyl applyingtime in each uptake shrinkage,

chloride solutions solution, by wool. percent solution seconds percentExample 3 A. A series of solutions were prepared containing varyingamounts of hexamethylene diamine in water. A minor proportion-about0.1%of the isooctylphcnyl other of polyethylene glycol was also added toeach.

B. Another series of solutions were prepared containing varying amountsof adipoyl chloride in various solvents.

Wool cloth was treated with the solutions in the following manner. Thecloth was immersed in one solution (A or B) for 15 seconds, squeezed toremove excess liquid, immersed for 15 seconds in the next solution (B orA), squeezed to remove excess liquid, rinsed in water, and dried in air.

The conditions employed and the results obtained are tabulated below.

TABLE III First treating solution, Second treating solu- Resin Area Runconcentration of active tion, concentration of uptake shrinkingredient,and active in redient, and on wool, t solvent used solvent used (pcr-(percent) ccn t) l-. Hexamethylenc di- Adipoyl chloride, 2 4. 9 8. 8

amine, 8.8 gJlOO ml. mlJlOO ml. carbon water. tetrachloride. 2 .doAdipoyl chloride 2 5.7 4.9

rnl./l00 ml. toluene. 3... Bore-methylene di- Adipoyl chloride, 1 3.612. 6

amine, 4.4 g./l00 ml. ml./l00 ml. carbon water. tetrachloride. 4-.--.Adipoyl chloride, 1 Hexemethylene di 2. 5 18.2

mL/lGO ml. carbon amine, 4.4 g./l00 nil. tetrachloride. water. 5---Hexairethylene di- Adipoyl chloride, 4 7.3 2.0

amine, 17.6 gJlOO nil/10G ml. carbon ml. Water. tetrachloride. =6"..-Adipoyl chloride. 4 Hoxamct-hylene di- 4. 8 2.0

mlJlOO ml. carbon amine, 17.6 gJlOO tetrachloride. ml. water.

16 Example 4 A. A series of solutions were prepared containing eitherhexaniethylcne diaminc or metaxylylenc diamine dissolved in water. Aminor pcrcentageabout 0.1 %--of the isooctylphcnyl ether of polyethyleneglycol was also added to each solution.

B. Another series of solutions was prepared containing terephthaloylchloride or scbacoyl chloride dissolved in carbon tetrachloride ormethylene chloride.

Wool cloth was treated with the solutions in the following manner: "hecloth was immersed in one solution (A or B) for a predetermined time,squeezed to remove excess liquid, immersed for a predetermined time inthe next solution (B or A), squeezed to remove excess liquid, and driedin air.

The conditions and the results are tabulated below TABLE IV Time ofFirst treating Second treating immer- Resin Area solution. 00113621-solution, conccnsion in uptake shrinkliun tration of active tration ofactive each on wool, one, ingredient, and ingredient, and solu- (per-(pur solvent used solvent used Lion, ccntl cent) seconds 1 TerephthaloylHexamethylenc co 1. G i). 0

chloride 2.5 diamine 17.6 ml. cargJlOO inl non tetrawater. chloride 2..d0 do .l 1. 5 4.0 3 -.dodo 3;] 0. ii 7.9 4 Metax'ylylene Sehscoylchlo- 60 4. 5 15.4

diemine 9 ride 2 mL/lOO mlJlOD ml. ml. carbon water. tetrachloride. 5Mctarylylene Sermcoyl ehlo- 15 1.4 20. 3

diaznine 4.5 ride 1 inL/IOO BIL/100 ml. ml. carbon water. tetrachloride.6 Terephthaloyl Met-axylylene 00 2. 2 19.0

chloride diuinino 8 g./ g./lo0 ml. 100 cc. waiter. methylene chloride.Control. 45

EMBODIMENT 2 In this embodiment of the invention, Component A is adiamine and Component B is a bischloroiormate. By such selection of thecomplementary agents, polyurethanes are deposited on the Wool fibers andgrafted thereto.

Particularly desirable features of this Embodiment 2 of the inventionare that a high degree of shrinkproofing is attained with a low level ofpolymer formed on the fiber. vioreover, the process is especially simplebecause the serial treatments may be carried out at ordinary (room)temperature, the polyurethane being formed virtually instantaneouslyunder such conditions.

Numerous variations of the basic procedure of this embodiment willsuggest themselves to those skilled in the art in the application ofEmbodiment 2 of the invention without departing from the fundamentals ofthe invention. Some of these variations are explained below.

If desired, one may prepare a prepolymer containing internal urethaneunits and terminal amino groups. Such prepolymcrs can be prepared, forexample, in known manner by reacting a molar excess of diaminc with abischloroformate. The prcpolyrncr would then be used as Component Awhile for Component B one would use a bischloroforrnatc. A typicalexample of procedure in this area would be to use as Component A aprepolymcr of the type HzNRNH- ORO-lNII-RNHJ and to use as Component B abischloroformate (ClCDGFJOOCCl) thus to produce a polymer containingrepeating units of the type R and R" represent bivalent orgroups. Such aprepolymer used as Component B in conjunction with a diamine asComponent 'A would yield a polyurethane similar to that shown above.

-It is evident from the foregoing description that there is a very widechoice available in: the selection'of the complementary agents (diamineand bischlorofor'mat'e) so that generically the polyurethanes deposited"on the Wool and grafted thereto will contain repeating units of thetype z N II R-N --ZR-ZC I l v t wherein R and R are bivalent organicradicals; Z represents an oxygen or sulphur atom;-and the xs takenseparately represent two hydrogen atoms or" two monovalent organicradicals, or, takentogether the xs' represent a single bivalent organicradical which links the two gen atoms to which they are attached. I

in the preferred modifications of the invention, 'Z is oxygen; R andR-'represent bivalent hydrocarbon radicals or bivalent hydrocarbonradicals interrupted by internal ether (-O-) linkages andx is hydrogen.In the especially preferred modifications of'the invention, thereactants are so chosen that R and R represents bivalent hydrocarbonradicals containing at least two carbon atoms. Coming under specialcondition particularly because of the exceptionally high shrinkresistance imparted with a very small proportion of polyurethane, arethe use of the following materials as thecomplementary agents.

Component A: Xylylene diamines or aliphatic alpha,

ethylene glycol bischloroforrnate, diethylene glycol bischloroformate,or hexane-1,6-di'ol bis'chloroformate.

This Embodiment 2 of, the invention isfurtherdemo-nstrated by thefollowingillustrative examples;

The tests for shrinkage referred to in the examples were conducted asdescribed above in the paragraphentitled Standard Shrinkage Test. Thecontrol (untreated) wool used in these examples had an area shrinkage of47 I Example 5 A. A solution was prepared containing 2% ofmetaxylylenediamine in water.

B. A' solution was: prepared containing glycol bischloroformate inbenzene.

A sample of wool cloth wasimmersed in solution A for 30 seconds, runthrough squeeze rolls to remove'excess liquid, immersed for 30'secondsinsolution B,.run through squeeze rolls to remove excess liquid, rinsed inwater, and dried in air at room temperature; The treated wool had apolyurethane resin uptake of 1.6% and on washing exhibited an areashrinkage of 107%. These 3% ofethylene nitrois results are tabulatedbelow, together with the shrinkage of the untreated wool sample;

Polyurethane resin deposited on Wool, percent Area shrinkage, percent 1None (control).

Example 6 The procedure of Example 5 was repeated using as solution A 3%ethylene glycol bischloroformate in benzene and as solution B, a 4l%solution of hexamethylene diamine water. I The following results wereobtained:

Polyurethane resin dep0s-' ited on wool,

-Area shrinkage, percent percent 1 None (control).

Example 7 The process of ExampleS was repeated using assolution A4%"heXamethylene'diamine in water and as solution B, a 3% solution ofethylene glycol bischloroformate in carbon tetrachloride. The followingresults were obtained:

Polyurethane resin depos- Area shrinkited on wool, age, percent Ipercent None (control) I Example 8 The process of Example 5 was repeatedusing as solution A- 4% hexamethylene diamine in water and'as solutionB; a 3% solution ofdiethylene glycol bisc'hloroforn'rate in carbontetrachloride. "The following results were obtained:

Polyurethane 1 resin depos- Area shrinkitetl on wool, age, percentpercent a Polyurethane resin depos- Area shrinkited on wool, wage,percent percent 1 None (control). 7

Example 10 The process of Example was repeated using as solution A 2%metaxylylene diamine in water and as solution B, a 3% solution ofdiethylene glycol bischloroformate 1 None (control).

Example 1 I A. A series of solutions were prepared containing 4%hexamethylene diamine (or 4% metaxylylene diamine), 4% Na CO and 0.1% ofa commercial wetting agent, the isooctylphenyl ether of polyethyleneglycol, in water.

B. Another series of solutions were prepared containing 3%1,6-hexanediol bischloroformate in benzene or carbon tetrachloride.

Wool cloth was treated with the solutions in the following manner: Thecloth was immersed in solution A for a predetermined time, squeezed toremove excess liquid, immersed for a predetermined time in solution B,squeezed to remove excess liquid, rinsed in water, and dried in air.

The conditions used and the results obtained are tabulated below:

(OCN- "-NCO) the type 0 0 -NH-R-NHd-NH-R'-NH-d-NH-R-NH- -NH-R NH-d- (Inthese formulas, R, R, and R" represent bivalent organic radicals.)

In the alterantive, one may prepare a prepolymer containing internalurea units and terminal isocyanate groups. Such a prepolymer used asComponent B in conjunction with a diamine as Component A would yield apolyurea similar to that shown above.

It is evident from the above description that there is a very Widechoice available in the selection of the complementary agents so thatgenerically the polyureas deposited onto the wool and grafted theretowill contain repeating units of the type Z z -NR-N NH-R'-NH lwhere R andR represent bivalent organic radicals; Z represents oxygen or sulphur;and the xs taken separately represent two hydrogen atoms or twomonovalent organic radicals, or, taken together they represent a singledivalent organic radical linking the two nitrogen atoms to which theseare attached. In the preferred modifications of the invention, Zrepresents oxygen; R and R represent bivalent hydrocarbon radicals orbivalent hydrocarbon radicals interrupted by internal ether (--0-)linkages; and x is by- Time of Resin up- I immersion take on Area RunFirst treating solution Second treating solution in each wool,shrinkage,

solution, percent percent sec.

1 4% hexamethylene diamine, 4'7 3% 1,6-hexanediol bischlorotormate 0 5.40

NazCOa, 0.1% of the isooctylphenyl in benzene. c of polyethylene glycolinwater. 2 do do 2.4 0 3 do 3% li-giexanediol bischlorotormato 30 4.6 1

111 l. 4 4% metnxylyleuedlamiue,4% NazCOz, 3% 1,6-hexanediolbischlorotormate 30 4.4 3.0

0.1% of the isooetylphenyl ether of polyethylene glycol in water. inbenzene. 5 (control)--- 47. 0

EMBODIMENT 3 In this embodiment of the invention, Component A is adiamine and Component B is a diisocy-anate. By such selection of thecomplementary agents, polyureas are deposited on the wool fibers andgrafted thereto.

Particularly desirable features of this Embodiment 3 of the inventionare that a high degree of shrinkproofing is attained with a low level ofpolymer formed on the fiber. Moreover, the process is especially simplebecause the serial treatments are carried out at ordinary (room)temperature, the polyurea being formed virtually instantaneously undersuch conditions.

Numerous variations of the basic procedure of this embodiment willsuggest themselves to those skilled in the art in the application ofEmbodiment 3 of the invention without departing from the fundamentals ofthe invention. Some of these variations are explained below.

If desired, one may prepare a prepolymer containing internal urea unitsand terminal amino groups. Such prepolymers can he prepared, forexample, in known manner by reacting a molar excess of diamine with adiisocyanate. The prepolymer would then be used as Component A while forComponent B one would use a diisocyanate. A typical example of procedurein this area would be to use as Component A a prepolymer of the type 0 0H=N--R-NHd-NH-W-NH-d-NH-R-NH, and to use as Component B a diisocyanatedrogen. In the especially preferred modifications of the invention, thereactants are so chosen that R and R represent bivalent hydrocarbonradicals containing at least two carbon atoms.

Coming under special consideration, particularly because of theexceptionally high shrink resistance obtained with very smallpercentages of polyurea, are the use (as Component A) of xylylenediamines or aliphatic alpha, omega diamine-s, particularly those of thetype Example 12 A. A solution was prepared containing 4% of hem--methylene diamine in water.

B. A solution was prepared containing 3%methylenebis(p-phenylisocyanate) in benzene.

A sample of wool cloth was immersed in solution A for a polyurea resinuptake of 1.7% and on washing inthe Accelerotor, exhibited an areashrinkage of 9.8%.

Example 13 I The process of Example 12 was repeated using as solution A4% hexamethylene diamine in water and as solution B a 3% solution ofmethylene-bis(p-phenylisocyahate) in carbon tetrachloride. The time ofimmersion of the cloth in each solution was 60 seconds. 7 p

The treated wool had a polyurea resin uptake of.2.4% and on washingexhibited an area shrinkage of 8.8%

Example 14 v The conditions and the results are tabulated below. N

First treating Second treating Resin Area solution, concen- 1 solutioneoncenuptake shrink- Run tration of active tration of active on 1 againgredient and ingredient and wool, percent solvent used solvent usedpercent 1 3% methylene 4% hexarnethy- 2. 2 5. 9

bis(p-phenyllone diamine in isocyanate) in water.

4. 2 4% metaxylylene 3% toluene di- 5. 4 7. 9

diamino in isocyanate in water. ben ene. 3 4% metaxylylene 3% toluene1i- 5. 20.0

. diamine in lsccyanate in ,r

I water. 4. 4 (control). 47.0

EMBODIMENT 4 In this embodiment of the invention, Component A-is a dioland Component B is a diacid chloride. By such selec tion of thecomplementary agents, polyesters are deposited on the Wool fibers andgrafted thereto.

Numerous variations in the basic procedure of this embodiment willsuggest themselves tothose skilled in the art in the application of theinvention without departing from the fundamentals of the invention. Someof these variations are explained below.

If desired, one may preparea prepoiymer. containing internal ester unitsand terminal hydroxy groups. .Such

prepolymers can be prepared, for example, in known HO-R'O ,-R' -OROH andto use as Component B a diacid chloride (ClCORfCOCl) thus to produce apolyester containing repeating units of the type H (In these formulas R,R, and R" represent bivalent organic radicals.)

In the alternative, one may'prepare a prepolymer containing internalesterunits and terminal carbonylchloride groups. Such a prepolymer usedas Component B in conjunction with a diol as Component A would yield apolyester similar to that shown above.

It is evident from the above description that there is a very widechoice available in the selection of the complementary agents sothatgenerically the polyesters deposited onto the wool andtgraftedthereto will contain repeating units of the type where R representsabivalent organic radical; Z represents an oxygen or sulphur atom; and Rfrepresents'a bivalent organic radical or a bond linking the two carbonylgroups. ln'jthepreferred modifications of the invention, Z is oxygen, Rand R represent bivalent hydrocarbon radicals or bivalent 'hydrocarbonradicals interrupted'by internal ether (O--) linkages; "In theespecially p're i e'rred modifications of the invention, thereactantsare s'o chosen that R and R represent bivalent hydrocarbon radicals containing at least two carbon atoms.

This Embodiment 4 of the invention is further dem'on strated by thefollowing illustrative examples.

The tests'for shrinkage referred to in Examples 15 to 18 were conductedas described above in the paragraph entitled Standard Shrinkage Test;The control (untreat-' ed) wool used in the experiments had an areashrinkage Example .15

- A. A solution was preparedcoutaining 4% of the so dium salt of2,2-bis(parahydroxyphenyl) propane, and 0.1% of a commercialwettingagent, the isooctylphenyl ether ofpolyethylene glycol, in Water. I, L A.I

B. A solution was prepared containing 3% .terephthalyl chloride inmethylchloroform. I a v A sarnpieof wool cloth was immersed in solution.A for seconds, run through squeeze rollersito remove excess liquid,immersed for60 seconds in solution B, run through squeeze rolls toremove excess liquid, rinsed with water, and dried in air.

The treated wool had a polyester resin uptake of 1% and .onwashingexhibited an area shrinkage of 21.7%.

Example 16 The procedure of Example 15 was repeated-using'as solution B3% sebacyl chloride in carbon tetrachloride. Two runs were made, in onecase holdingthe wool 30 seconds in each solution, in the other holdingthe wool 60 seconds in each solution. The results are tabulated be low:

, Residence, Polyester Area Run time in each resin dep0sshrinkage,

'- solution, see. ited onwool, percent;

A y, percent 1. so i I 1.9 22:6 2 y 60 as 20.8

- Example 17 23 The following results were obtained:

Polyester Area resin deposshrinkage, ited on wool, percent percentExample 18 (l) A sample of wool cloth was immersed for 30 seconds in asolution of 3% sebacyl chloride in carbon tetrachloride. The cloth wasrun through squeeze rolls to remove excess liquid, then immersed for 30seconds in a solution containing 5% of the potassium salt of ethyleneglycol (KOCH CH OK) in isopropyl alcohol. The cloth was run throughsqueeze rolls to remove excess liquid, rinsed with water, and dried inair.

(2) A sample of wool cloth was immersed for 120 secends in a solutioncontaining 5% of the potassium salt of ethylene glycol in isopropylalcohol. The cloth was run through squeeze rolls to remove excessliquid, then immersed for 120 seconds in a solution of 3% terephthalylchloride in carbon tetrachloride. The cloth was run through squeezerolls to remove excess liquid, rinsed with water, and dried in air.

The results are tabulated below:

Polyester resin Area Run deposited on shrinka e,

Wool, percent percent Example 19 {tree shrinkage, percent Sample Example15 Examrlc 16, run 1 Example 16. run 2 Example 17 Example 18, run 1Example 18, run 2 Untreated contr EMBODIMENT In this embodiment of theinvention, Component A is a diol and Component B is a bischloroformate.By such selection of the complementary agents, polycarbonates aredeposited onto the wool fibers and grafted thereto.

Numerous variations in the basic procedure of this embodiment willsuggest themselves to those skilled in the art in the application of theinvention without dcparting from the fundamentals of the inventions.Some of these variations are explained below.

If desired, one may prepare a prepolymer containing internal carbonateunits and terminal hydroxy groups. Such prepolymers can be prepared, forexample, in known manner by reacting a molar excess of diol with ahischloroformate. The prepolymer would then be used as Component A whilefor Component B one would use a bischloroformate. A typical example inthis area would he to use as Component A a prepolymer of the type OH0R-o( ioR'-0i 0-R-0H and to use as Component B a bischloroformate(ClCOOR"COOC1) thus to produce a polycarbonate containing repeatingunits of the type it OROiiOR'0iiO-ROi JO-R"0C (In these formulas, R, R,and R represent organic radicals.)

In the alternative, one may prepare a prepolymer containing internalcarbonate units and terminal OCOCl groups. Such a prepolymer used asComponent B in conjunction with a diol as Component A would yield apolycarbonate similar to that shown above.

It is evident from the above description that there is a very widechoice available in the selection of the complementary agents so thatgenerically the polycarbonates deposited onto the wool and graftedthereto will contain repeating units of the type -ZRZ-( 2--Z--R-Z-i 3-wherein Z represents an oxygen or sulphur atom; R and R representbivalent organic radicals. In the preferred modifications of theinvention, Z is oxygen; R and R represent bivalent hydrocarbon radicalsor bivalent hydrocarbon radicals interrupted by internal ether (O-)linkages. In the especially preferred modifications of the invention thereactants are so chosen that R and R represent bivalent hydrocarbonradicals containing at least two carbon atoms.

This Embodiment 5 of the invention is further demonstrated by thefollowing illustrative examples.

The tests for shrinkage referred to in the examples were conducted asdescribed above in the paragraph entitled Standard Shrinkage Test. Thecontrol (untreated) wool used in the experiment had an area shrinkage of47%.

Example 20 A sample of wool cloth was immersed for 60 seconds in a 6%solution of the sodium salt of 2,2-bis(3-methyl- 4-hydroxyphenyl)propane in water. The cloth was run through squeeze rolls to removeexcess liquid, then immersed for 60 seconds in a solution containing 5parts by Volume of the bischloroformate of hexane-1,6-diol dissolved inparts by volume of a petroleum solvent containing 96% aromatics, 1%parafiins, and 3% naphthenes, specific gravity 0.87, boiling range314-352 F. The cloth was run through squeeze rolls to remove excessliquid, rinsed with water, and dried in air.

The treated wool had a polycarbonate resin uptake of 4.2% and on washingexhibited an area shrinkage of 20%.

Example 21 The procedure of Example 20 was repeated with the exceptionthat the second treatment solution contained 5 parts by volume of thebischloroformate of 2,2-dimethyl-propanediol-l,3 in 100 parts by volumeof the petroleum solvent.

The treated wool had a polycarbonate resin uptake of 3.6% and on washingexhibited an area shrinkage of 23.5%.

Example 22 A sample of wool cloth was immersed for 60 seconds in a 6%solution of the sodium salt of 2,2-bis(3-isopropyl- 4-hydroxyphenyl)propane in water. The cloth was run through squeeze rolls to removeexcess liquid, then immersed for 60 seconds in a solution containing 5parts by volume of the bischloroformate of 2,2-dimethyl-propanediol-1,3in 100 parts by volume of the petroleum solvent described in Example 20.The cloth was run through squeeze rolls to remove excess liquid, rinsedwith water, and dried in air.

'and dried in air.

. Example 23 I A sample of wool cloth Was'immersed for 60 seconds 'in a6% solution of the sodium salt of 2,2-bis(4-hy'droxyphenyl) propaneinwater. The cl-othwas run through squeeze rolls to remove excess liquid,then immersed for 60 seconds in a solution containing 5 parts by volumeof squeeze rolls to remove excess liquid,'rinsed with water,

The treated wool hadfla' polycarbonate'r'esin uptake of 1.3% and onwashing exhibitedan area shrinkage INTERPOLYMERS: 1

In accordance with fErnbodirnents 6, .and tl,

polymers are formed in situ on wool fibers and grafted thereto. Thein-terpoly ners produced inaccordance with these embodiments contain intheir recurring structural elements at least two different unitsselected from the category of amideyurethane, ,ure'a, .esten andcarbonate units, these units being linked togetherthrough carbon atoms.The types of different unitsin the interpolyrner I are determined by thereactants applied to the wool fabric.

In a typical example of the invention, adiarninea diacid chloride, andbischloroformate are applied to the fabric whereby the interpolymerfonned contains both amide and urethane groups, hence is referred to asa copoly (amide-urethane). 'Th formation of this interpolymer may beillustrated as follows: v y

ll. ll Diacid chloride ClC-RG-Cl Bischlorofor'mate ClC-O--R +C'-G1Oopoly (amideurethan'e) l 1 0 -NH-RNH-il-R- NHRNH+t .lO-R O and 4HC1 (Inthe above, and following formulae R, R, andfR" represent bivalentorganic radicals.)

It will be observed that the above interpolyrner contains the amide j 1v I T if (CNH) and urethane (NI-I--( JO-) V units linked through thebivalent radical R. These units are underlined in the above formula ofthe interpolymer.

Other illustrative examples of interpolymers which can be produced onwool fibers in accordance with the invention are given below. The unitsin pointare underlined.

Copoly (amide-urea):

Copoly (amide-ester):

Copoly (urethaneurea):

the bischloroformate of hexane-l,'6-diol dissolved in 100 10 'partsby'volume ofbenzene. The cloth Was'run through Copoly(carbonate-urethane):

Copoly (ester-carbonate) of U ,79 fQ t1 fQ r --Q% 2* :2

.Otherpossi ble combinations willibe obvious towthose skilled-g in theart," from the above exemplifications. Moreover, the inter-polymers neednot contain, only two differentu its, they may contain more than twodifferent units,,.as for, example} terpoly (amide-.urethaneaurea), terpoly (arnide-urea-ester), terpoly (amide-urethane-,car'- bona te), orother. combination of thevaforcsaid amide, urethane, urea, .ester,,,andcarbonate units. ,1 v Generically; the interpolymers produced'inaccordance -wtih the invention may-be described as interp'olyrnerswherein the: recurring, structures contain at least two different unitsof the category amide, urethane, urea, ester, and carbonate, thesevunitsbeingv linked. through carbon atoms; These interpolymers can thus bedesignated by the formulae i t wherein X, X, X", X, X"representthe'diiferent units (amide, urethane urea, ester, or'carb'onateand Q represents the divalent'radicals 'linking'the units together. Itwill be evident from the following descriptionthat the values of Q ,(aswell as the values 'of X',"X etc.) will depend'on the nature of thereactants chosen fo r jfori nin-g the inter-polymers. As "disclosedbelow, these reactants may be chosen from a wideivariety of categoriesso that generically -Q" represents a bivalent organic radical. Morespecifically, and preferably, the reactants re chosen so thatQ're'prese'nt's a bivalent'hydrocarbon radical o'r'a' bivalenthydrocarbon radical interrupted by internal ether ('O') linkages. In anespecially referred modification of the invention, the reactants arechosen so that Q represents bivalent hydrocarbon 'radicals containing atleast two carbon atoms. Generally, excellent results are obtained withthe "interpolymers containing two differentunitsand among these the oneswhich provide particularly good shrink-proofing effects with low levelsof interpolyme-r deposits are those of the types Carbonate:

wherein Z is oxygen or sulphur.

In the practice of this aspect of invention, selection is first made ofthe appropriate complementary agents herein termed Component A andComponent Brequired to produce the desired interpolymer. Theinterrelationship between the nature of the agents to be used asComponents A and B and the type of interpolymer produced are explainedin detail below in connection with the different modifications of theinvention. However, it is apropos to mention at this point that ingeneral, Component A may be a diamine, a diol, or a mixture of a diamineand a diol. Dependent on the materials selected for Component A,Component B may be a diacid chloride, a bischloroformate, adiisocyanate, or mixtures of these classes of compounds. Since the aimin every case is to produce an interpolymer, the selection of materialsmust include this proviso: Taken together, Components A and B mustinclude reagents of at least three classes. For example, if Component Aincludes both a diamine and a diol then Component B may rep resent anyone of the classes of diacid chlorides, bischloroformates, ordiisocyanates. A typical example in this area would be to use a mixtureof a diamine and a diol as Component A and a diacid chloride asComponent B, whereby the resin eventually formed would he a copoly(amide-ester). If, however, Component A is a diamine (or a diol) thenComponent B would need to include at least two reagents of ditferentclass, for instance, a diacid chloride and a bischloroformate, a diacidchloride and a diisocyanate, or other combinations of any two or more ofthe group diacid chlorides, bischloroformates, and diisocyanates. Atypical example in this area would be to use a diamine as Component Aand a mixture of diacid chloride and diisocyanate as Component B,whereby the resin eventually formed would be a copoly (amide'urea). Theguiding factors involved in the selection of materials for Components Aand B to produce a desired interpolymer will be evident to those skilledin the art from the above general description and the detailedinformation set forth hereinafter.

Having selected Components A and B, these agents are applied to wool inthe same manner as employed for the polymers previously described.

EMBODIMENT 6 EMBODIllIENT 6.COMPONENT A: DIAMINE Component B 1l'nterpolymer formed Diacid chloride and bischloroformate- Dist-idchloride and diisocyanate..."

Bischloroformute and diisocyanate.-.

Diacid chloride. bischloroformate.

and diisocyanate.

Copoly (amide-urethane). Copoly (amide-urea).

Copoly (urethane-urea). Terpoly (amldeurethane-urea).

As noted hereinabove, in this Embodiment 6 of the invention, it isnecessary that Component B include at least two of the classes ofbifunctional compounds. Thus Component B may be a mixture of diacidchloride and bischloroformate or a mixture of diacid chloride anddiisocyanate or a mixture of bischloroformate and diisocyanate or amixture of diacid chloride, bischloroformate and diisocyanate. Therelative amounts of these reactants of difierent class may be varieddepending on the character of the interpolymer to be produced. Forexample, in using a mixture of diacid chloride and bischloroformate asComponent B, the proportion of amide to urethane groups in theinterpolymer may be increased by increasing the proportion of diacidchloride used in the mixture. In many cases it is preferred to employthe reagents in equimolar proportions, thus to provide an interpolymerhaving an equal number of different units. For example, by using anequimolar mixture of a diacid chloride and a bischloroformate asComponent B, the resulting interpolymer will contain substantially equalnumber of amide and urethane units. However, the use of equimolarmixtures is by no means critical and one may use any mixture containing10 to (molar basis) of the reagent of one class and the remainder (90 to10%) of the reagents of the other classes.

Numerous variations in procedure will suggest themselves to thoseskilled in the art in the application of Embodiment 6 of this invention,without departing from the fundamentals of the invention. Some of thesevariations are explained below.

If desired, one may prepare a prepolymer containing internal amide (orurethane or urea) units and terminal amino groups. Such prepolymers canbe prepared, for example, by reacting in known manner a molar excess ofdiamine with a diacid chloride, bischloroformate, or diisocyanate. Theprepolymer would then be used as Component A while for Component B onewould use any one of the reagents (diacid chloride, bischloroformate ordiisocyanate) which was not used in preparing the prepolymer. Thus,taking into account the variation in the internal units of the polymer,the following alternatives are among those possible.

COMPONENT A: PREPOLYMER CONTAINING INTERNAL AMIDE UNITS AND TERMINALAMINO GROUP-3 Component B Inter-polymer formed Bischloroformate Copoly(amide-urethane). Dusocyanate Copo1y(aznidc-urea).

COMPONENT A: PREPOLYMER CONTAINING INTERNAL URETHANE UNITS AND TERMINALAMINO GROUPS Component B Interpolymer formed Diacid chloride.- Copoly(urethane-amide). Dusocyanate-- Copoly (urethane-urea).

COMPONENT A: PREPOLYMER CONTAINING INTERNAL UREA UNITS AND TERMINALAMINO GROUPS Component B Interpolymer formed Diacid chloride Copoly(urea-amide) Bischloroformate Copoly (urea-urethane).

A typical example of procedure in this area would be to use as ComponentA a prepolymer of the type thus to produce an interpolymer containingamide and urethane units of the type A typical exampleof procedureinthis area would be to use as Component A a prepolyme-r of the typeHzN-R-NH- 0 RO (.7-'-NH-RNH2 and to use as Component 3 a diacid chloride(ClCOR'-'COCI) I thus to produce an interpolymer containing amide andurethane units of the type s w v I natural ste a -etumn nmtniut Thisprinciple of using prepolymers could be in other ways as well.Forfexamplega li ol could be canor bischloroformate) to producealprepolymer con ain.

ing internal ester or carbonate) funitls] terminal and 'tis QmN -R' HQas Component A one could depositon'the wool fibers acopoly (ester-urea)containingrecurringunits of. the type Another example ofthissystem'is'touse as Component B- a compound containing internal carbonateunits and terminal'is'ocyanate groups, havingthe'formula 0 a ooR-NooThis compound used in conjunction with H R--NH as Component A vwouldyield a copoly (carbonate-urea) containing recurring units of theftype Afurther example of this system is to employ as Component B a compoundcontaining internal carbonate units j and terminal carbonyl chloridegroups, having the formula 0' o "-"o g nu- I '01- R-OOO -R-OG.O- -R O-..Cl, thi compound used, in c njnnct iolIIWith N -R 'L NH as ComponentAWill 'yield a copoly (carbonate-amide) containing recurring units ofthe type This Embodiment 6 of the invention is further demonstratedbyLthe followingillustrative,examples The shrinkage tests referred to inthe'example's were carried outas described above in the-paragraphentitled de'rise d: inknown' manner with an'excessjofdia cid chlorideStandard Shrinkage Test. The control (untreated) wool used in theseexperiments had an area shrinkage of 47%.

The petroleum solvent referred to in the examples was a commercialhydrocarbon mixture having the following characteristics: 96% aromatics,parafiins, 3% naphthenes; specific gravity 0.87; boiling range 314-362F.

The commercial wetting agentreferred to in the examples was theisooctylphenyl ether of polyethylene glycol.

The toluene diiso'cyanatereferred to in Examples 29 and 30 was toluene2,4-diisocyanate. I

Example 24.C0p0ly (Amide-Urethane) Component A; Diarnine. y I ComponentB: Diacidchlorideand vbischloroformate. A sample of wool cloth wasimmersed for 30 seconds in a solution containing 4g. hexan 1ethylenediamine and ,8; g; Na CQ per ,100 ml. water and50.1%l of a commeni t Wetn a e Th sl t .w r m d from ibis o 1 u;tion, run through squeeze rollsto removeexcess liquid, then immersed for 30 secondsinza solutioncontaininglj ml. sebacyl chloride and 1.5 ml. hexane-1,6- diol'bischlo1'oormate per. 100 ml, petroleum, solvent. The jcloth was:removed from this solution, run through squeeze rolls to remove excessliquid, rinsed in water, and dried in air.

The following results were obtained:

Interpqlymer resin Area shiiukdeposited age,-perc,cnt

on wool, percent ina solution containing 4 g. hexamethylene diarnine and8. g.- N CO per 100. mlrwater and 0.1% of-a commercial etting-agent. Thecloth was removedifrom this solution, runthrough squeeze rolls toremove'excess liquid, then'immersed fo'r30 seconds ina solutioncontaining 1.5 ml. sebacyl chlorideand 1.5 ml. diethyleneglycolv-bischloroformate per IOOmIwbenZene; The cloth 'was removed from thissolution, run through squeeze rolls to remove excess liquid, rinsed inwater, .and dried in air. I s

The following results were obtained:

Interpolymer I resin Area shrink- I deposited agapercent on wool,

percent Example 26.- Co p 0-ly (Amide-Urethane) Component A: Mixture ofdiamines. I I I l Component B: Diacid chloride and bischloroformate. Asample ofwool cloth was immersed for 30 seconds in 'asolu'tioncontaining 2 g. hexamethylene diamine. and

2' mlf meta-xylylene dia'mine per 100 Water and 0.1%

of a commercial wetting agent. f The cloth was'removed from thissolution, run'through squeeze rolls toremov'e excess liquid, thenimmersed for 30 seconds in a'solution 'containi'nglj mlfsebacyl'chlorideand 1.5 ml. hexanel,6-diol bischlorof-ormate per 100 mi. petroleumsolvent.

The cloth-"was removed from this solution, runthro'u'gh squeeze rolls;to remove and dried in air.

excess liquid," rinsed water,

The following results were obtained:

Interpolymer resin Area shrinkdeposited age, percent on wool, percentExample 27.-Copoly (Amide-Urea) Component A: Diamine.

Component B: Diacid chloride and diisocyanate.

A sample of wool cloth was immersed for 30 seconds in a solutioncontaining 4 g. hexamethylene diamine and 8 g. Na CO per 100 ml. waterand 0.1% of a commercial wetting agent. The cloth was removed from thissolution, run through squeeze rolls to remove excess liquid, thenimmersed for 30 seconds in a solution containing 1.5 ml. sebacylchloride and 1.5 g. methylene bis (pphenylisocyanate) per 100 ml.benzene. The cloth was removed from this solution, run through squeezerolls to remove excess liquid, rinsed in water, and dried in air.

The following results were obtained:

Interpolymer resin Area shrinkdeposited age, percent on wool, percentExample 28.Cpoly (Amide-Urea) Component A: Diamine.

Component B: Diacid chloride and diisocyanate.

A sample of wool cloth was immersed for 30 seconds in a solutioncontaining 4 g. metaxylylene diamine and 8 g. Na CO per 100 ml. waterand 0.1% of a commercial wetting agent. The cloth was removed from thissolution, run through squeeze rolls to remove excess liquid, thenimmersed for 30 seconds in a solution containing 1.5 ml. sebacylchloride and 1.5 g. methylene bis (p-phenylisocyanate) per 100 ml.benzene. The cloth was removed from this solution, run through squeezerolls to remove excess liquid, rinsed in water, and dried in air.

The following results were obtained:

Interpolymer resin Area shrinkdeposited age, percent on wool, percentExample 29.Cop0ly (Amide-Urea) Component A: Diamine.

Component B: Diacid chloride and diisocyanate.

A sample of wool cloth was immersed for 30 seconds in a solutioncontaining 4 g. hexamethylene diamine and 8 g. Na CO per 100 ml. waterand 0.1% of a commercial wetting agent. The cloth was removed from thissolution, run through squeeze rolls to remove excess liquid, thenimmersed for 30 seconds in a solution containing 1.5 ml. sebacylchloride and 1.5 m1. toluene diisocyanate per 100 ml. benzene. The clothwas removed from this solution, run through squeeze rolls to removeexcess liquid, rinsed in water, and dried in air.

The following results were obtained:

Interpolymer resin deposited on wool, percent Area shrlnkage, percentExample 30.--C0p0ly (Urethane-Urea) Component A: Diamine. Component B:Bischloroformate and diisocyanate. A sample of wool cloth was immersed'for 30 seconds in a solution containing 4 g. hexamethylene diamine and8 g. Na CO per ml. water and 0.1% of a commercial wetting agent. Thecloth was removed from this solution, run through squeeze rolls toremove excess liquid, then immersed for 30 seconds in a solutioncontaining 1.5 ml. toluene diisocyanate and 1.5 ml. hexane- 1,6-diolbischloroformate per 100 ml. benzene. The cloth was'removed from thissolution, run through squeeze rolls to remove excess liquid, rinsed inwater, and dried in air.

The following results were obtained:

Interpolymer resin Area shrinkdeposltcd age, percent on wool percentExample 31.C0p0ly (Urethane-Urea) Component A: Diamine.

Component B: Bischloroformate and diisocyanate.

A sample of wool cloth was immersed for 30 seconds in a solutioncontaining 4 ml. meta-xylylene diamine and 8 g. Na CO per 100 ml. waterand 0.1% of a commercial wetting agent. The cloth was removed from thissolution, run through squeeze rolls to remove excess liquid, thenimmersed for 30 seconds in a solution containing 1.5 g. methylene bis(p-phenylisocyanate) and 1.5 ml. hexane-1,6-diol bischloroformate per100 ml. benzene. The cloth was removed from this solution, run throughsqueeze rolls to remove excess liquid, rinsed in water, and dried inair.

The following results were obtained:

Iuterpolymer resin Area shrinkdeposlted age, percent on wool, percentEMBODIMENT 7 EMBODIMENT 7.-COMPONENT A: DIOL Component B Inter-polymerformed Copoly (ester-carbonate).

Copoly (ester-urethane). Copoly (carbonate-urethane). Terpoly(ester-carbonate'urethane) Diacid chloride and bischloroformate Diacidchloride and diisocyanate Bisehloroformate and diisocyanate- Diacidchloride. blschloroiormate.

and diisocyanate As noted above, the objects of Embodiment 7 of thepresent invention are attained by using as Component B a mixture ofdiacide chloride and bischloroformate or a mixture of diacid chlorideand diisocyanate or a mixture of bischloroformate and diisocyanate or amixture of diacid chloride, bischloroformate, and diisocyanate. It isevident that with regard to Component B of this embodiment, the sameconsiderations are applicable as in Embodiment 6 described above.

That is, all the information set forth above in describing the compoundssuitable for use as Component B of Embodiment 6, the proportions ofthese compounds, the conditions of reaction, etc., is equally applicablein the present embodiment.

Numerous variations in procedure will suggest themwives to those skilledin the art in the application of Embodiment 7 of this invention withoutdeparting from the fundamentals of the invention as described herein.Some of these variations are explained below.

If desired, one may prepare a prepolymer containing internal ester (orcarbonate or urethane) units and terminal hydroxy groups. Suchprepolymers can be prepared for example, by reacting in known manner amolar excess of diol with a diacid chloride, bischloroformate, ordiisocyanate. The prepolymer would then be used as Component A while forComponent B one would use any one of the reagents (diacid chloride,bischloroformate, or diisocyanate) which was not used in preparing theprepolymer. Thus, taking into account the variation in the internalunits of the prepolymer, the following alternatives are among thosepossible.

COMPONENT A: PREPOLYMER CONTAINING INTERNAL ESTER UNITS AND TERMINALHYDROXY GROUPS Component B Interpolymer formed Bischloroformate Gopoly(ester-carbonate). Diisocyanate Cop-01y (ester-urethane).

COMPONENT A: PREPOLYMER CONTAINING INTERNAL OARBONATE UNITS AND TERMINALHY- DROXY GROUPS Component B Interpolymer formed Oopoly(carbonate-ester). Oopoly (carbonate-urethane).

Diacid chloride. Diisocyanate COMPONENT AzPBEPOLYMER CONTAINING INTERNALURETHANE UNITS AND TERMINAL IIY- DROXY GROUPS.

Component B Inter-polymer formed Diacid chloride Bischloroformate Copoly(urethaneester). Copoly (urethane-carbonate) A typical example of thisprocedure in this area would be to use as Component A a prepolymer ofthe type:

and to use as Component B, a bischloroformate (CIOCOR"OCOC1) o I! -o.-o1

groups and/ or terminal ll ---0 Gr-Ql groups. This prepolymer used asComponent B in conjunction with a diol as CompDnfint A would yield aninterpolymer containing both ester and carbonate units.

This Embodiment 7 of the invention is further dem onstrated by thefollowing illustrative examples.

The shrinkage tests referred to in the example were carried out asdescribed above in the paragraph entitled Standard Shrinkage Test. Thecontrol (untreated) wool used in these experiments had an area shrinkageof 47%.

The commercial wetting agent referred to in the examples was theisooctylphenyl ether of polyethylene glycol.

The petroleum solvent referred to in the examples was a commercialhydrocarbon mixture having the following characteristics. 96% aromatics,3% naphthene-s, 1% para ffins; specific gravity 0.87; boiling range314-362" F.

Example 3Z.C0p0ly (Ester-Carbonate) Component A: Diol.

Component B: Diacid chloride and bischloroformate.

A sample of wool cloth was immersed for 60 seconds in a solutioncontaining 10 g. of 2,2-bis (4-hydroxy-dibromophenyl) propane per 100ml. of water, with addition of suttficient sodium hydroxide to dissolvethe hisphenol, and 0.1% of a commercial wetting agent. The cloth wasremoved from this solution, run through squeeze rolls to remove excessliquid, then immersed for 60 seconds in a solution containing 1.5 ml.sebacyl chloride and 1.5 ml. -hexane-1,6.-diol bischloroformate per 10.0ml. petroleum solvent. The cloth Was removed from this solution, runthrough squeeze rolls to remove excess liquid, rinsed in water, anddried in air.

The following results were obtained:

Interpolymer resin Area shrinkdeposited age, percent on Wool, percent 7'Example 33.-C0p0ly (Ester-Carbonate) Component A: Diol.

'Component B: Diacid chloride and bischloroformate.

A sample of wool cloth was immersed for 60 seconds in a solutioncontaining 5 g. of 2,2-bis (3-methy1-4-hydroxyphenyl) propane per 100ml. of water, with addition of sufficient sodium hydroxide to dissolvethe bis- Interpolymer I resin Area shrinkdeposited age, percent on wool,

percent 35 EMBODIMENT s EMBODIMENT S.COMPONENT A: DIAMINE AND DIOLComponent B Interpolyrncr formed Diacid chloride. Copoly (amide-ester).Bischlorofonnate- Copoly (urethane-carbonate). Drisocyanate Copoly(uren'urcthanc Diacid chloride and bischloroformate. Diacid chloride anddiisoeyanatm- Tet-rspoly (amide-urethane-cstercarlonate) 'letrapcly(amide-uzctlianc-urca) ester).

In formulating Component A for practice of Embodiment 8 of theinvention, one may use any of the diamines and diols set forth above.The relative amounts of diamine and diol which comprise Component A maybe varied depending on the character of the interpolymer to be produced.For example, in a system using a diacid chloride as Component B, theproportion of amide to ester units in the interpolymer may be increasedby increasing the ratio of diamine to diol in Component A.

In many cases it is preferred to employ the diamine and diol inequirnolar proportions, thus to provide an interpolymer having any equalproportion of difierent units. For example, by using an equimolarmixture of diamine and diol as Component A and a bischloroformate asComponent B, the resulting interpolymer will contain substantially anequal ratio of carbonate and urethane units. However, the use ofequimolar proportions is by no means critical and one can use asComponent A any mixture containing to 90% (molar basis) of diamine andthe remainder (90 to 10%) diol.

With regard to Component B, one may use a diacid chloride,bischloroformate, diisocyanate, or mixtures of these. The types ofinterpolymer resulting from different values chosen for Component B areexemplified in the initial paragraph of the description of thisembodiment of the invention.

Numerous variations in procedure will suggest themselves to thoseskilled in the art in the application of Embodiment 8 of this invention,without departing from the fundamentals of the invention as taughtherein. Some of these variations are explained below.

Ifi desired, one may use as Component A, a single compound containingterminal hydroxy and amino groups, for example, 2-aminoethanol,3-aminopropanol, 4-aminobutanol, 6-aminohexanol, S-aminooctanol,o-aminophenol, m-aminophenol, p-aminophenol, para (4-aminopheny1)phenol, etc. Then, by suitable selection of Component B, variousinterpolymers may be formed on the Wool. Some of the possiblealternatives in this system are given below.

COMPONENT A: COMPOUND CONTAINING TERMINAL AMINO AND TERMINAL HYDROXYGROUPS Component B Intcrpolymer formed Diacid chloride Copoly(esteramide). Bischloroformate.-. Copoly (carbonate-urethane).Diisocyanate Copoly (urethane-urea).

The shrinkage tests referred to in the examples were carried out asdescribed above in the paragraph entitled Standard Shrinkage Test. Thecontrol (untreated) wool used in these experiments had an area shrinkageof 47%.

The commercial wetting agent referred to in the examples was theisooctylphenyl ether of polyethylene glycol.

The petroleum solvent referred to in the examples was a commercialhydrocarbon mixture having the following characteristics: 96% aromatics,3% naphthenes, 1% paralfins; specific gravity 0.87; boiling range314-362 F.

Examples 34 and 36.C0p0ly (Amide-Ester) Component A: Dlamine and diol.Component B: Diacid chloride.

(34) A solution was prepared containing 2 g. hexamethylene diamine, 5 g.2,2-bis(3-methyl-4-hydroxyphenyl) propane, 1.5 g. NaOH and 4.0 g. Na COper 100 ml. water and 0.1% of a commercial wetting agent. A sample ofwool cloth was immersed for 60 seconds in the solution, then removed,run through squeeze rolls to remove excess liquid and immersed for 60seconds in a second solution containing 3 ml. sebacyl chloride per 100ml. benzene. The cloth was removed from the second solution, run throughsqueeze rolls to remove excess liquid, rinsed in water and dried in air.

(35) Wool cloth was treated as in Ex. 11 above except that the secondsolution contained 3 g. terephthalyl chloride per 100 ml. benzene.

The results are tabulated below:

Component A: Diamine and diol.

Component B: Bischloroformate.

A sample of wool cloth was immersed for 60 seconds in a solutioncontaining 2 g. hexamethylene diamine, 5 g. 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 1.5 g. NaOH and 4 g. Na 'CO per 100ml. water and 0.1% of a commercial wetting agent. The cloth was removedfrom this solution, run through squeeze rolls to remove excess liquid,then immersed for 60 seconds in a solution containing 3 ml.hexane-1,6-diol bischloroformate per 100 ml. benzene. The cloth wasremoved from this solution, run through squeeze rolls to remove excessliquid, rinsed in water, and dried in air.

The following results were obtained:

Interpolyrner resin Area shrinkdepositcd age, percent 021 wool, percentEXAA4PLE 3 7 .C0p0ly (Carbonate- Urethane) solvent. The cloth wasremoved from the second solunon, run through squeeze rolls to removeexcess liquid, rinsed in water and dried in air.

The results are tabulated below:

Interpolymer resin Area shrinkdeposited age, percent on wool,

percent This application is a continuation-in-part of our copendingapplications listed below:

Serial No. 90,604, filed February 10, 1961, entitled Shrinkproofing ofWool with Polyamides (which in turn is a continuation-impart of SerialNo. 22,651, filed April 15, 1960);

Shrinkproofing of Wool with Polycarbonates.

The prior applications referred to above (Ser. No. 22,651, Ser. No.83,848, Ser. No. 85,438, S'er. No. 88,232, Ser. No. 88,233, and Ser. No.90,604) have been abandoned.

Although the present invention finds its greatest field of utility inthe shrinkproofing of wool and is peculiarly adapted for such usebecause of a combination of important factory-including the advantagesthat a high degree of shrink resistance is imparted with a minor amountof polymer, that the shrinkproofing treatment does not significantlyimpair the hand of the wool, that the treatment does not impair otherdesirable fiber characteristics such as tensile strength, elasticity,porosity, etc., that the polymer is grafted to the wool molecules sothat the shrinkproofing efiect is exceedingly durable and is retainedeven after long Wear and repeated launderingit is evident that theinvention may be extended to other areas. Thus the principles of theinvention may be extended to forming polymers in situ on othersubstrates besides Wool, particularly substrates of a fibrous structure.Typical examples of such materials are animal hides, leather; animalhair; cotton; hemp; jute; ramie; fiax; Wood; paper; synthetic cellulosicfibers such as viscose, cellulose acetate, cellulose acetate-butyrate;casein fibers; polyvinyl alcohol-protein fibers; alginic fibers; glassfibers; asbestos; and organic non-cellulosic fibers such as poly(ethylene glycol terephthalate), polyacryonitrile, polyethylene,polyvinyl chloride, polyvinylidene chloride, etc. Such applications ofthe teachings of the invention may be for the purposes of obtainingfunctional or decorative effects such as sizing, finishing, increasinggloss or transparency, increasing water-repellancy, increasingadhesionor bonding-characteristics of the substrates with rubber,polyester resins, etc. It is not claimed that in such extensions of ourteachings shrinkp-roofing would be attained nor that graft polymerswould be produced. However, it might be expected that graft polymerswould be formed with proteinous substrates such as animal hair, animalhides, and the like.

Attention is called to the fact that the present application is one of aseries of applications filed by us generally concerned withshrinkproofing wool wherein various types of condensation polymers areformed on and grafted to the wool fibers. Condensation polymers broadlyand polyamides specifically are the subjects of the present application;polyurethanes are the subject of Serial No. 99,319, filed March 29,1961; polyureas are the subject of Serial No. 100,476, filed April 3,1961;

polyesters are the subject of Serial No. 101,599, filed April 7, 1961;polycarbonates are the subject of Serial No. 102,323, filed April 11,1961; and interpolymers are the subject of Serial No. 109,229 filed May10, 1961.

Having thus described the invention, what is claimed is:

1. A process for shrinkproofing wool without significant impairment ofits hand, which comprises serially impregnating wool with two solutions,one solution containing a diamine dispersed in Water, the other solutioncontaining a diacid chloride dispersed in an inert, volatile,essentially water-immiscible solvent, the said diamine and diacidchloride reacting to form in situ on the Wool fibers .a resinouspolyamide.

2. The process of claim 1 wherein the diamine has the formula wherein nhas a value from 6 to 10.

3. The process of claim 1 wherein the diacid chloride has the formulawherein n has a value from 4 to 10.

4. The process of claim 1 wherein the diamine is hexamethylene diamine.

5. The process of claim 1 wherein the diacid chloride is adipoylchloride.

6. The process of claim '1 wherein the diacid chloride is sebacoylchloride.

7. A process for shrinkproofing wool without significant impairment ofits hand, which comprises serially impregnating wool with two solutions,one containing a diamine in a first solvent, the other containing adiacid chloride in a second solvent, said first and second solventsbeing substantially mutually immiscible, the said diamine and diacidchloride reacting to form in situ on the Wool fibers a resinouspolyamide.

8. A modified wool fiber which exhibits improved shrinkage properties ascompared with the unmodified wool fiber comprising wool fiber having apolyamide formed in situ thereon and chemically bonded to the Wool.

9. A modified wool fiber which exhibits improved shrinkage properties ascompared with the unmodified wool fiber comprising Wool fiber having apolyamide of a diamine and a dicarboxylic acid formed in situ thereonand chemically bonded to the Wool.

10. The product of claim 9 wherein the polyamide contains recurringstructural groups of the formula wherein n has a value from 4 to 10 andm has a value from 6 to 10.

11. A process for treating a fibrous material which comprises seriallydepositing on said fibrous material in superposed phases in interfacialrelationship a pair of complementary, direct-acting, organic,polyamide-forming intermediates, at least one of said phases beingliquid, the said intermediates directly reacting under said conditionsto form a polyamide in situ on said material.

12. A process for treating a fibrous material which comprises seriallyapplying to said fibrous material a pair of complementary,direct-acting, organic, polyamideforming intermediates in separateliquid phases of limited mutual solubility.

13. A process for treating a fibrous material which comprises seriallydistributing on the surface of the fibrous elements of said material apair of complementary, direct-acting, organic, polyamide-formingintermediates in superposed phases of limited mutual solubility, atleast one of said phases being liquid, the said intermediates reactingunder such conditions to form a polyamide in situ on said fibrouselements.

14. A process for treating wool which comprises serially distributing onthe surface of the wool fibers a pair of complementary, direct-acting,organic, polyamideforming intermediates in superposed liquid phases oflimited mutual solubility, said intermediates reacting rapidly undersaid conditions to form a polyamide in situ on said fibrous elements andgrafted thereto.

15. A process for treating a fibrous material which comprises seriallyimpregnating a fibrous material with two solutions, one solutioncontaining one member of a pair of complementary, direct-acting,organic, polyamideforming intermediates in a first solvent, the othersolution containing the complementary member of said pair ofcomplementary, direct-acting, organic, pol /amideforming intermediatesin a second solvent, the first and second solvents being substantiallymutually immiscible, the said pair of intermediates reacting rapidlyunder said conditions to form in situ on the fibers a resinouspolyamide.

16. The process of claim 15 wherein the members of said pair ofcomplementary, direct-acting, organic, polyamide-forming intermediatesare a diamine and a diacid chloride.

References Cited in the file of this patent UNITED STATES PATENTS2,522,338 Angus et a1 Sept. 12, 1950 2,526,948 Himel Oct. 24, 19502,537,064 Kropa et al Jan. 9, 1951 2,565,259 Nyquist et al. Aug. 21,1951 2,644,773 Hammer et a1. July 7, 1953 2,684,305 Quinlivan July 20,1954 2,696,448 Hammer et a1 Dec. 7, 1954 2,862,836 Oosterhout Dec. 2,1958 2,929,737 Tischbein et al. Mar. 22, 1960

11. A PROCESS FOR TREATING A FIBROUS MATERIAL WHICH COMPRISES SERIALLYDEPOSITING ON SAID FIBROUS MATERIAL IN SUPERPOSED PHASED IN INTERFACIALRELATIONSHIP A PAIR OF COMPLEMENTARY, DIRECT-ACTING, ORGANIC,POLYAMIDE-FORMIING INTERMEDIATES, AT LEAST ONE OF SAID PHASED BEINGLIQUID, THE SAID INTERMEDIATES DIRECTLY REACTING UNDER SAID CONDITIONSTO FORM A POLYAMIDE IN SITU ON SAID MATERIAL.